JPH10125976A - Photosensor and its photoconduction layer forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To supply a fixed performance stably by causing a photoconduction layer to contain a specific bisazo compound. SOLUTION: A photosensor containing a bisazo compound represented by formula I in formula I, X1 and X2 represent a halogen atom, a substituted or unsubstituted alkyl radical, a substituted or unsubstituted alkoxy radical, a nitro radical, a cyano radical, a hydroxy radical or substituted or unsubstituted amino radical respectively, and at least one of X1 and X2 is a halogen atom. p and q represent integers of 0, 1, or 2 respectively, and do not become zero simultaneously. And when p and q are two, X1 and X2 may be the same or different radicals respectively. 'A' represents a radical represented by formula II. (In formula II, Ar represents an aromatic carbocyclic radical or aromatic complex cyclic radical having a fluoride hydrocarbon radical. Z represents a group of nonmetallic atoms necessary for forming a substituted or unsubstituted aromatic carbocyclic radical or aromatic complex cyclic radical. m and n represent integers of 0, 1 or 2 respectively. But m and n do not become zero simultaneously.} is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical sensor capable of recording optical information in the form of visible information or electrostatic information on an information recording medium, and a material for forming a photoconductive layer thereof.

[0002]

2. Description of the Related Art In order to record optical information on an information recording medium, an optical sensor comprising a photoconductive layer provided with an electrode on the front surface, and a charge holding layer provided on the rear surface with an electrode opposed to the optical sensor. And an information recording medium comprising on the optical axis,
A method of exposing while applying a voltage between both electrodes, recording an electrostatic charge on the charge holding layer according to the incident optical image, and developing the electrostatic charge with a toner or reproducing with a potential reading device, for example, It is described in JP-A-1-290366 and JP-A-1-289975. Further, the charge holding layer in the above method is a thermoplastic resin layer, the electrostatic charge is recorded on the surface of the thermoplastic resin layer, then heated, and the electrostatic charge recorded by forming a frost image on the surface of the thermoplastic resin layer. A method for visualizing is described in, for example, JP-A-3-1
No. 92288.

Furthermore, the present applicants have disclosed that the information recording layer in the information recording medium is a liquid crystal-polymer composite type liquid crystal recording layer, which is exposed when a voltage is applied in the same manner as described above, and which is exposed to an electric field formed by an optical sensor. The information recording and reproducing method of reproducing information as visible information by transmitted light or reflected light when reproducing information is described in Japanese Patent Application Nos. Hei 4-3394 and Hei 4-24722.
And Japanese Patent Application No. 5-266646. This information recording / reproducing method can visualize recorded information without using a deflection plate.

[0004] The present applicant has found that in the above-mentioned information recording system, by making the optical sensor semiconductive and having an amplifying action, it is possible to improve the information recording performance on an information recording medium. First, Japanese Patent Application No. 6
Although the application was filed as Japanese Patent No. -6437, there is a demand for providing an optical sensor that has stable information recording performance and that can withstand repeated use.

[0005]

SUMMARY OF THE INVENTION The present invention relates to an optical sensor used for forming information on an information recording medium and a material for forming a photoconductive layer thereof, which is capable of stably supplying a constant performance. An object of the present invention is to provide an optical sensor which can be manufactured and has excellent durability and a material for forming a photoconductive layer thereof.

[0006]

A first optical sensor according to the present invention is an optical sensor having a photoconductive layer on at least an electrode, and is disposed to face an information recording medium having at least an information recording layer on the electrode. In a light sensor capable of applying a voltage in a state of being exposed between both electrodes or exposing in a state of applying a voltage and forming information on an information recording medium by an electric field or a charge amount, The photoconductive layer contains a bisazo compound represented by the following general formula (1).

[0007]

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In the formula, X ₁ and X ₂ each represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxy group or a substituted or unsubstituted amino group; Represents a group,
At least one of X ₁ and X ₂ is a halogen atom.

P and q each represent an integer of 0, 1 or 2; p and q are not simultaneously 0; and when p and q are 2, X ₁ and X ₂ are the same or It may be a different group. A represents a group represented by the following general formula (2).

[0010]

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(Wherein, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having a fluorinated hydrocarbon group; Z represents a substituted or unsubstituted aromatic carbocyclic group or an aromatic heterocyclic group) M and n each represent an integer of 0, 1 or 2. However, m and n do not become 0 at the same time. ｝.

A second optical sensor according to the present invention is an optical sensor having a photoconductive layer on at least an electrode, and is disposed so as to face an information recording medium having an information recording layer on at least the electrode. Voltage or apply
Alternatively, exposure is performed with a voltage applied, and in an optical sensor capable of forming information by an electric field or a charge amount on an information recording medium, in a photoconductive layer in the optical sensor,
It is characterized by containing an imidazole perylene compound represented by the following structural formula (3) or (4).

[0013]

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The optical sensor of the present invention is semiconductive, and when a voltage is applied while exposing between both electrodes, or when an exposure is performed with a voltage applied, the information recording medium is exposed to light. It is possible to record information with an intensity that is greater than or equal to the current flowing, and also shows the behavior that the conductivity gradually decreases when the voltage is continuously applied even after the exposure is completed,
It has the function of continuing to record information on the information recording medium.

Further, the above-mentioned optical sensor of the present invention is
^When a voltage with an electric field strength of ⁵ to 10 ⁶ V / cm is applied,
The passing current density in the unexposed area is 10 ⁻⁴ to 10 ⁻⁷ A / cm ²
It is characterized by being.

The photoconductive layer forming material in the first optical sensor of the present invention is such that an optical sensor having a photoconductive layer on at least an electrode and an information recording medium having an information recording layer on at least the electrode are opposed to each other. A photoconductive sensor in a photosensor that is arranged and applies a voltage between both electrodes in an exposed state, or can be exposed in a state where a voltage is applied to form information on an information recording medium by an electric field or a charge amount. A layer forming material, characterized by containing a bisazo compound represented by the general formula (1).

Further, in the photoconductive layer forming material in the second photosensor of the present invention, the photosensor having at least the photoconductive layer on the electrode and the information recording medium having the information recording layer on at least the electrode are opposed to each other. A photoconductive sensor in a photosensor that is arranged and applies a voltage between both electrodes in an exposed state, or can be exposed in a state where a voltage is applied to form information on an information recording medium by an electric field or a charge amount. A layer forming material, characterized by containing the imidazole perylene compound of the structural formula (3) or (4).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photosensor according to the present invention is formed by laminating a photoconductive layer on an electrode, and the photoconductive layer is a single layer type and a stacked type in which a charge generation layer and a charge transport layer are stacked. The photoconductive layer generally has a function of generating photo-induced charge carriers (electrons and holes) at an irradiated portion when irradiated with light, and allowing these carriers to move in a layer width. In the present invention, a specific azo compound described below is contained in the photoconductive layer in the case of a single-layer type, and in the charge generation layer in the case of a multilayer type, thereby providing an optical sensor. When light is applied to the information recording medium, the electric field or charge applied to the information recording medium is amplified over time with the light irradiation, and the increased conductivity gradually attenuates when voltage is applied even after the light irradiation is completed. While maintaining the electric field or the amount of electric charge to the information recording medium, not only stably exhibiting a certain electric property, but also having good film properties and repeated use. It can be an optical sensor with little deterioration.

A description will be given of the photo-induced current amplifying action of the optical sensor according to the present invention. A gold electrode of 0.16 cm ² is laminated on the photoconductive layer of the optical sensor for measuring an amplification effect. A constant DC voltage is applied between the two electrodes with the ITO electrode as a positive electrode, and 0.5 seconds after the start of the voltage application, light is irradiated from the substrate side for 0.033 seconds, and the current value of the optical sensor during the measurement time is measured. At the start of light irradiation (t = 0)
Measure from. The irradiation light was a green light obtained by a green filter (manufactured by Nippon Vacuum Optical Co., Ltd.) using a xenon lamp (L2274 manufactured by Hamamatsu Photonics) as a light source.
The intensity of irradiation light irradiated at the intensity of looks was measured with an illuminometer (manufactured by Minolta), and the characteristics of the filter used are shown in FIG.

When light is irradiated at this light intensity, the transparent substrate, I
Considering the light transmittance of the TO film and the spectral characteristics of the filter, 4.2 × 10 ¹¹ photons / cm ² seconds enter the photoconductive layer. When all the incident photons are converted into optical carriers, a photocurrent of 1.35 × 10 ⁻⁶ A / cm ² per unit area is theoretically generated. Here, when measuring with the measuring device, the ratio of the photo-induced current actually generated in the optical sensor to the theoretical photo-current, that is, apparent quantum efficiency = (photo-induced current actually generated in the optical sensor) Value / theoretical photocurrent value) is defined as the apparent quantum efficiency of the optical sensor. The light-induced current is a value obtained by subtracting a base current value, which is a current flowing in a portion not irradiated with light, from a current value of a light irradiation portion. The current that flows due to
This is different from a so-called photocurrent. The photo-induced current amplification action in the photo-sensor of the present invention is defined as such a behavior of the photo-induced current.

An optical sensor having a photo-induced current amplifying action and an optical sensor having no photo-induced current amplifying action (hereinafter referred to as a comparative sensor) according to the present invention will be described with reference to the measurement results obtained by the measuring apparatus. . First, an example of the measurement result of the comparative sensor is shown in FIG. In FIG.
The (m) line is the theoretical value (1.35 × 10 ⁻⁶ A / cm ² ).
Indicates a state in which light irradiation was performed for 0.033 seconds and voltage application was continued after light irradiation. The line (n) is an actual measurement line of the comparative sensor, and the increase of the photocurrent during light irradiation is small, and the value does not exceed the theoretical value (1.35 × 10 ⁻⁶ A / cm ² ). The quantum efficiency is only up to about 0.4. FIG. 7 shows changes in quantum efficiency during light irradiation.

On the other hand, in the optical sensor of the present invention, as shown in FIG. 8, as an example, the light-induced current increases upon irradiation with light, as shown in FIG. It can be seen that the quantum efficiency exceeds 1 at 01 seconds, and the quantum efficiency continues to increase thereafter.

Further, in the comparative sensor, the photocurrent abruptly attenuates at the same time as the end of the light irradiation. Therefore, even if a voltage is continuously applied after the light irradiation, a current effective as optical information cannot be obtained. On the other hand, in the optical sensor of the present invention, by continuing the voltage application even after the light irradiation, the photoinduced current flows continuously while gradually attenuating, and the photoinduced current can be subsequently taken out. Optical information can be continuously obtained.

Although the detailed reason is unknown, in the optical sensor of the present invention, all of the photo-induced charge carriers generated by the irradiation of the information light are generated in the direction of the width of the photoconductive layer in a voltage applied state. Instead of moving, some of the photoinduced charge carriers are trapped in the trap sites existing in the photoconductive layer or at the interface between the electrode and the photoconductive layer, and the trapped charges accumulate over time. It is considered that in the state where a voltage is applied, in addition to the photocurrent generated by exposure, an injection current from the electrode induced by the trapped charges flows, and the apparent photoinduced current is amplified with time. Can be However, this phenomenon occurs when charge carriers are appropriately injected from the electrode to the charge generation layer, and when appropriate injection is not performed, that is, when injection is too small or injection is too large. There is almost no amplification effect.

In the present invention, by using an optical sensor containing a charge generating agent in the photoconductive layer, charge carriers are appropriately injected from the electrode to the charge generating layer, and a photo-induced current amplifying action is effectively generated. be able to. When the exposure is completed while maintaining the voltage applied state, the photocarriers generated by the exposure are immediately attenuated and disappear, but the decay of the trapped charges is slow, so that the induced carriers are induced by the trapped charges. It is presumed that a sufficient amount of the injected current flows from the electrodes while attenuating, and the attenuation gradually occurs. This photo-induced current is an effect of current amplification triggered by light in the optical sensor of the present invention,
Since a current larger than a photocurrent caused by incident light expected from a normal photosensitive member flows, it is possible to effectively provide optical information to an information recording medium.

On the other hand, a photosensitive element used for general electrophotography has a dark resistivity of 10 ¹⁴ to 10 ¹⁶ Ω ·
cm, the photosensor of the present invention cannot achieve its purpose in electrophotography, and a photosensor having a photoconductive layer having a large dark resistivity for general electrophotography is: It cannot be used for the purpose of the present invention.

The specific resistance ρ (Ω · cm) of the optical sensor
And the current density J (A / cm ² ), the film thickness of the optical sensor is d, the electrode area is S, and the applied electric field strength is E (V / c).
m), ρ = (E · d / J · S) × (S / d) =
Since the relational expression of E / J holds, the specific resistance ρ (Ω · c
m) can be obtained from the applied electric field strength and the current density, and in each embodiment of the present invention, is expressed by the current density.

An electrophotographic photoreceptor containing a specific bisazo compound represented by the general formula (1) or an imidazole perylene compound represented by the structural formulas (3) and (4) is known (Japanese Patent Application Laid-open No. JP-A-2-20877, JP-A-7-26
No. 1436), the present inventors have studied to improve the optical sensor as described above, and as a result, the general formula (1)
A specific bisazo compound represented by the formula (3),
The inventor has found that the incorporation of the imidazole perylene compound represented by (4) stably exerts the specific performance as an optical sensor, leading to the present invention.

The bisazo compound represented by the general formula (1) contained in the photoconductive layer in the first optical sensor of the present invention is preferably represented by the following general formulas (5) and (6).
(7) and (8).

[0030]

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In the formula, X _1a , X _1b , X _2a and X _2b each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group or a hydroxy group. Or a substituted or unsubstituted amino group, and among X _1a , X _1b , X _2a and X _2b ,
At least one is a halogen atom. X _1a , X _1b , X
_2a and X _2b may be the same or different groups. Ar ′ has the same meaning as Ar in the general formula (1). Y has the same meaning as the substituent of Z in the general formula (1). Hereinafter, specific examples of the bisazo compound represented by the general formula (1) in the present invention will be described, but the bisazo compound in the present invention is not limited thereto.

Specific exemplified compounds

[0033]

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[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7]

[0041]

[Table 8]

[0042]

[Table 9]

[0043]

[Table 10]

[0044]

[Table 11]

[0045]

[Table 12]

[0046]

[Table 13]

[0047]

[Table 14]

[0048]

[Table 15]

[0049]

[Table 16]

[0050]

[Table 17]

[0051]

[Table 18]

[0052]

[Table 19]

The bisazo compound represented by the general formula (1) in the present invention can be easily synthesized by a known method, and is described, for example, in JP-A-2-20877.

Next, the first optical sensor of the present invention will be described. FIG. 1 is a cross-sectional view for explaining a stacked optical sensor, in which 13 is an electrode, 14 ′ is a charge generation layer,
4 "is a charge transport layer and 15 is a substrate.

The charge generation layer 14 ′ is formed by the above general formula (1)
The bisazo compound represented by the fine particles in a suitable medium, after adding a binder as necessary, on the electrode, for example, blade coating method, dip coating method, spinner coating method, slide coating method, α coating method, After being applied by a kiss coating method, a roll coating method or the like, it is formed by drying. The bisazo compound is preferably dispersed with a primary average particle size of 1 μm or less, preferably 0.7 μm or less, and most preferably 0.5 μm or less.

The binder is not particularly limited.
A hydrophobic, high dielectric constant, insulating polymer compound is preferable, and various thermoplastic or thermosetting synthetic resins can be suitably used. For example, silicone resin, polycarbonate resin, vinyl acetal resin such as vinyl formal resin, vinyl butyral resin, styrene resin, styrene-butadiene copolymer resin, epoxy resin, acrylic resin, saturated or unsaturated polyester resin, methacrylic resin, vinyl chloride Resin, vinyl acetate resin, vinyl chloride
A vinyl acetate copolymer resin and the like can be mentioned, and they can be used alone or in combination.

In the ink composition for forming a photoconductive layer in the laminated optical sensor, the mixing ratio of the bisazo compound and the binder is such that the binder is added to 0.1 part by weight of the bisazo compound.
The ratio may be 10 to 10 parts by weight, preferably 0.2 to 1 part by weight. Examples of the medium include 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, tetrahydrofuran, cyclohexanone, dioxane, 1,2,3-trichloropropane, ethylcellosolve, 1,1,1, -trichloroethane, Examples include methyl ethyl ketone, chloroform, toluene, xylene,
The solid content is reduced by ball mill dispersion, disperser dispersion, sand mill dispersion, three-roll dispersion, ultrasonic dispersion and the like.
2% to 20% by weight, preferably 1% to 5% by weight
It is said.

The charge generation layer has a thickness of 0.01 after drying.
２2 μm, and preferably 0.1-0.5 μm. With such a film thickness, good sensitivity and image quality are exhibited.

The charge transporting layer 14 "is formed by dispersing or dissolving a charge transporting substance in a suitable medium described in the charge generating layer, coating the charge transporting substance on the charge generating layer 14 ', and drying. It is preferable to use a binder unless the charge-transporting substance is a substance such as poly-N-vinyl carbazole or polyglycidyl carbazole which plays a role of a binder by itself. It is a substance having good transport properties of carriers generated in, for example, oxadiazole, oxazole, triazole, thiazole, triphenylmethane, styryl, pyrazolone, hydrazone, aromatic amine, carbazole , Polyvinylcarbazole, Stilbene, Enamine, Azine, Triphenylamine, Butadier And a polycyclic aromatic compound, a stilbene dimer, a biphenyl, and the like, and it is necessary to use a substance having good hole transporting properties.

As the binder, those similar to the binder in the charge generation layer described above, and further, a polyarylate resin and a phenoxy resin can be used, and a styrene resin, a styrene-butadiene copolymer resin, and a polycarbonate resin are preferable. Binder is charge transporting substance 1
0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight
It is desirable to use in a proportion of 1 part by weight.

The charge transport layer has a thickness of 1 to 50 μm after drying.
m, preferably 3 to 20 μm, whereby good sensitivity and image quality can be obtained. In addition, any of the above-described charge transporting substances which can be formed into a film by an evaporation method can be formed alone without using a binder.

Next, a single-layer type optical sensor will be described. FIG. 2 is a cross-sectional view for explaining the single-layer type optical sensor, in which 13 is an electrode, 14 is a photoconductive layer, and 15 is a substrate. In order to form a single-layer photoconductive layer, the above-described charge transporting substance may be dissolved or dispersed in the above-described dispersion for forming a charge generation layer, and may be similarly coated on an electrode. The charge-transporting substance can be arbitrarily selected, but it is preferable to use the binder described in the above-mentioned laminated optical sensor, except for using the substance which itself serves as a binder as described above.

In the ink composition for forming a photoconductive layer in a single-layer optical sensor, the mixing ratio of the bisazo compound and the binder was set such that the amount of the binder was 0.1 to 1 part by weight of the bisazo compound.
The ratio may be 1 to 10 parts by weight, preferably 0.3 to 3 parts by weight.

The charge transporting substance is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 3 parts by weight, per 1 part by weight of the bisazo compound represented by the general formula (1). When the charge transporting substance is not allowed to function as a binder, the binder is 0.1 to 10 parts by weight with respect to 1 part by weight of the total amount of the bisazo compound and the charge transporting substance.
Preferably, it is used in a ratio of 0.1 to 1 part by weight.

As the medium in the ink composition, the medium described in the above-mentioned laminated optical sensor is exemplified.
By the same dispersing method, the solid content is adjusted to 0.2 to 20% by weight, preferably 1 to 5% by weight.

The photoconductive layer in the single-layer type optical sensor has a thickness after drying of 5 μm to 30 μm, preferably 1 μm to 30 μm.
The thickness is preferably 0 to 20 μm, whereby good sensitivity and image quality can be obtained.

The electrode 13 in the optical sensor needs to be transparent if the information recording medium described later is opaque, but may be transparent or opaque if the information recording medium has transparency. Materials that stably provide a specific resistance of ⁶ Ω · cm or less, for example, metal thin film conductive films such as gold, platinum, zinc, titanium, copper, iron, and tin, tin oxide, indium oxide, zinc oxide, titanium oxide, and tungsten oxide A metal oxide conductive film such as vanadium oxide, an organic conductive film such as a quaternary ammonium salt, or the like can be used alone or as a composite material of two or more types. Among them, metal oxide conductors are preferable, and indium tin oxide (ITO) is particularly preferable. The electrode is formed by a method such as vapor deposition, sputtering, CVD, coating, plating, immersion, and electric field polymerization, and is formed on the entire surface between the information recording layer and an arbitrary pattern. Further, two or more kinds of materials can be stacked and used.

The substrate 15 needs to have transparency if the information recording medium described later is opaque. If the information recording medium has transparency, it may be either transparent or opaque. It has the shape of a film, tape, disk, or the like, and strongly supports the optical sensor. If the optical sensor itself has a supporting property, it is not necessary to provide it. However, the material and thickness are not particularly limited as long as the optical sensor has a certain strength capable of supporting the optical sensor. For example, a flexible plastic film, or a plastic sheet or card of glass, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polymethyl acrylate, polyester, polycarbonate, or the like is used.

If the electrode 13 is transparent, a layer having an anti-reflection effect can be laminated on the other surface of the substrate on which the electrode 13 is provided, or the anti-reflection effect can be exhibited, if necessary. It is advisable to provide an antireflection property by adjusting the thickness of the transparent substrate or by combining the two.

Next, the second optical sensor of the present invention will be described. The imidazole perylene compound represented by the structural formulas (3) and (4) to be contained in the photoconductive layer in the second optical sensor of the present invention will be described.

The imidazole perylene compounds represented by the structural formulas (3) and (4) can be used in a photoconductive layer in a Cu—Kα
6.3 ± 0.2 ° of X-ray diffraction spectrum with respect to X-ray, 1
2.4 ± 0.2 °, 25.3 ± 0.2 °, 27.1 ±
A crystal having a peak at 0.2 °, 12.4 ±
The peak intensity at 0.2 ° is the maximum, and at the same time, the half width of the peak is 0.65 ° or more, and 11.5 ± 0.2
It preferably exists without showing a clear peak at °.

The crystal form of the imidazole perylene compound is described in J. Imag., Vol. 33, pp. 151-159 (1989).
Four types of X-ray diffraction spectra called ε and ρ are disclosed. Basically, α-type and ε-type have similar crystal structures, but it is clear that ρ-type is a completely different crystal. The crystal state in the present invention is based on this ρ type. The change in state that occurs in the step of dispersing and pulverizing the ρ-type crystal in an organic solvent has a significant effect on the sensitivity characteristics.

In general, in order to obtain high-sensitivity optical sensor characteristics, first, it is necessary to obtain a uniform coating film in which the charge generating substance is atomized. That is, the first important thing in the dispersion atomization step is to atomize the charge generating substance.

When the crystallite size becomes smaller than a certain size due to dispersion atomization, broadening of a diffraction peak and reduction in peak intensity occur in the X-ray resolution spectrum. The ρ-type crystal of the imidazole perylene compound has an X-ray diffraction spectrum for Cu-Kα ray,
6.3 ± 0.2 °, 12.4 ± 0.2 °, 25.3 ±
It is characterized by peaks at 0.2 ° and 27.1 ± 0.2 °, but there is also a unique peak at 11.5 ± 0.2 °. If the ρ-type crystal is dispersed and refined, broadening of the entire peak can be seen. Particularly important in the present invention is that the half width of the peak at 12.4 ± 0.2 ° is 0.65 °. The peak at 12.4 ± 0.2 ° broadened in this manner resulted in 1
The peak at 1.5 ± 0.2 ° is buried, and 11.5
It is necessary that the peak is not recognized in the range of ± 0.2 °. However, if the half width of the peak at 12.4 ± 0.2 ° exceeds 1.5 °, it cannot be said that the crystal is in a ρ-type crystal state.

The photosensor characteristics of the imidazole perylene compound according to the present invention depend on the crystal state characterized by the relative intensity of the peak in the X-ray diffraction spectrum. In many cases, the imidazole perylene compound has a peak intensity around 6.3 ° or a maximum at the stage of synthesis, and a sublimated compound has a peak intensity of 25 to 28 ° at a maximum and a peak at 12.4 °. The strength may be maximum. However, when these are dispersed and atomized in an organic solvent, the relative intensity of each peak changes, and thus the characteristics of the optical sensor change, but the crystal in the present invention has a peak at 12.4 ± 0.2 ° in the X-ray diffraction spectrum. By setting the strength to be the maximum, particularly excellent sensitivity characteristics can be obtained.

That is, in the present invention, 12.4 of the ρ-type crystal is used.
The half width of the peak of ± 0.2 ° or 0.65 ° or more,
In addition, a state where the peak intensity at 12.4 ± 0.2 ° is maximum after the particles are atomized to a state that does not show a clear peak at 11.5 ± 0.2 ° is used.

The method for obtaining such a crystalline state of the imidazole perylene compound is not particularly limited. However, the imidazole perylene compound purified by sublimation is subjected to an acid paste treatment (amorphization or low crystallization) using sulfuric acid, and this is subjected to affinity. It is intended to form a desired crystal state while growing crystals by gentle dispersion in a highly volatile organic solvent with a polymer binder interposed. In this method, uniform atomization is achieved, and a reduction in characteristics due to the introduction of crystal defects can be avoided due to a small mechanical impact.

The imidazole perylene compound of the structural formula (3) or (4) can be synthesized by a dehydration condensation reaction between perylene-3,4,9,10-tetracarboxylic dianhydride and o-phenylenediamine. The synthesized imidazole perylene compound is subjected to sublimation purification to remove impurities. The sublimation operation is repeated once to about 5 to 6 times, but it is preferable to repeat the sublimation two or more times. When a coating solution is prepared without performing sublimation purification, it is difficult to obtain the crystalline state in the present invention. The imidazole perylene compound obtained by sublimation shows a sharp peak pattern in the X-ray diffraction spectrum, confirming that the compound has a high crystallinity.

The imidazole perylene compound having a high crystallinity obtained by sublimation purification is converted to a state with a low crystallinity by performing an acid paste treatment using sulfuric acid. That is, after dissolving in concentrated sulfuric acid, the solution is poured into a poor solvent such as water or methanol to cause precipitation, which is filtered and dried to obtain fine particles of low crystalline fine particles.
The low crystal powder after the acid paste treatment is subjected to a dispersion treatment in a solvent having a high affinity for the imidazole perylene compound by using a suitable disperser. Examples of the solvent having a high affinity include a ketone solvent having 4 to 8 carbon atoms or a solvent having 4 carbon atoms.
Use of a cyclic ether solvent of from 7 to 7 or a halogenated hydrocarbon solvent of from 2 to 4 carbon atoms is useful. Among them, particularly preferred solvents include methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone,
Examples thereof include tetrahydrofuran, dichloroethane, and trichloroethane. In this dispersion treatment, good results can be obtained by the presence of an appropriate binder polymer.

Particularly desirable binder polymers include:
Polyvinyl acetal resin such as polyvinyl butyral and polyvinyl formal, vinyl chloride-vinyl acetate resin, polyester resin, polycarbonate resin, acrylic resin and methacrylic resin, acrylic and methacrylic copolymer resin, silicone resin, silicone copolymer resin, polystyrene, styrene copolymer Examples thereof include a polymer resin, a phenoxy resin, a phenol resin, a urethane resin, and an epoxy resin.

In the dispersion coating liquid obtained by such a method, the specific crystalline state in the present invention is realized. In this method, high purification by sublimation purification is important for adjusting the crystal state during dispersion, and this is further made amorphous by acid paste treatment with sulfuric acid. In the process of dispersion treatment, the amorphous state (or low crystalline state) is obtained. ), The crystal is grown by a specific solvent effect, whereby a specific crystal state in the present invention can be stably obtained.

An optical sensor is manufactured using the obtained dispersion coating solution. Whether or not the crystalline state of the present invention is realized in the photoconductive layer can be confirmed by measuring the X-ray diffraction spectrum of the imidazole perylene compound peeled from the optical sensor. Since the crystal state does not change in the process of coating the photoconductive layer, it can be confirmed by removing the solvent from the dispersion coating solution and measuring the X-ray diffraction spectrum.

These samples are measured by a powder X-ray diffractometer using Cu-Kα radiation as an X-ray source, and a diffraction line intensity distribution is obtained as a function of the black angle 2θ. At this time, if the sample amount is sufficient, the relative intensity ratio between the peak intensities does not change depending on the sample amount, but as the sample amount decreases, the peak intensity on the low angle side relatively increases. Therefore, in the measurement, a sufficient amount of the sample must be used so that the peak intensity ratio does not change with the sample amount.

The peak intensity here is, as shown in FIG. 10, the starting point of the intersection d between the line segment connecting the rising points a and b from the baseline level including noise and the perpendicular drawn from the vertex c. It is defined by the height to the vertex c (the length of the line segment cd). The half width of the peak is defined as the peak value at a position at a height of cd / 2 from the point d.

The second optical sensor of the present invention uses the dispersion coating liquid whose crystal state has been adjusted in place of the above-mentioned charge generation layer coating liquid in the first optical sensor, thereby providing the first light sensor. As in the case of the sensor, a stacked optical sensor and a single-layer optical sensor may be prepared.

Next, an information recording medium used in combination with the optical sensor of the present invention will be described. Examples of the information recording medium include a case where the information recording layer is a liquid crystal-polymer composite (hereinafter, referred to as LCPC). LCPC
Has a structure in which resin particles are dispersed in a liquid crystal phase,
As the liquid crystal material, a smectic liquid crystal, a nematic liquid crystal, a cholesteric liquid crystal, or a mixture thereof can be used. As a liquid crystal, from the viewpoint of so-called memory properties, it retains its orientation and retains information permanently.
It is preferred to use smectic liquid crystals.

Examples of the smectic liquid crystal include a liquid crystal material exhibiting a smectic A phase such as a cyanobiphenyl-based, cyanoterphenyl-based, phenylester-based, and fluorine-based liquid crystal material having a long carbon group as a terminal group of a substance exhibiting liquid crystallinity. A liquid crystal substance exhibiting a smectic C phase used as a liquid crystal, a liquid crystal substance exhibiting a smectic H, G, E, G phase, or the like can be given.

As a material for forming the resin particles, for example, a UV-curable resin which is compatible with the liquid crystal material in a monomer or oligomer state, or a solvent common to the liquid crystal material in a monomer or oligomer state The one having compatibility with is preferably used. Examples of such an ultraviolet-curable resin include acrylic acid esters and methacrylic acid esters. In addition, a solvent-soluble resin having compatibility with a common solvent with the liquid crystal material, for example, an acrylic resin, a methacrylic resin, a polyester resin, a polystyrene resin, and a copolymer containing these as a main component,
Epoxy resins, silicone resins and the like can be mentioned.

The content ratio of the liquid crystal material and the resin is such that the content of the liquid crystal is 10% by weight to 90% by weight, preferably 40% by weight.
The content is preferably used so as to be 80% by weight. If it exceeds 90% by weight, phenomena such as oozing out of liquid crystal occur, and image unevenness occurs, which is not preferable.

Since the thickness of the information recording layer affects the resolution, the thickness after drying is 0.1 μm to 10 μm, preferably 3 μm.
The operating voltage can be reduced while maintaining high resolution. If the film thickness is too small, the contrast of the information recording portion is low, and if it is too large, the operating voltage is undesirably high.

Next, two information recording devices using this information recording medium and the above-described optical sensor will be described.

First, in the first information recording apparatus, as shown in FIG. 3, the information recording medium 2 uses the above-described optical sensor 1 and an insulating resin film spacer 19 such as a polyimide film, and has a thickness of 2 μm to 20 μm. And the electrodes 13 and 13 'are connected via a voltage source V to form an information recording device. One or both of the electrodes 13 and 13 'in this device may be transparent.

Further, a second information recording device as shown in FIG. 4 may be used. FIG. 4 is a cross-sectional view of the information recording apparatus. In the figure, reference numeral 20 denotes a dielectric layer, and the same reference numerals as those in FIG. 3 indicate the same contents.

In this information recording device, the optical sensor 1 and the information recording medium 2 are stacked with no gap therebetween, with the dielectric layer 20 interposed therebetween. This information recording device is particularly suitable when the photoconductive layer in the optical sensor is formed by applying a solvent. That is, when the information recording layer is directly applied and formed on the photoconductive layer, the liquid crystal in the information recording layer elutes due to the interaction between them, and the image due to the elution of the photoconductive material by the solvent for forming the information recording layer. The occurrence of unevenness can be prevented. In addition, the optical sensor and the information recording medium can be integrated.

In forming the dielectric layer 20, it is necessary that the constituent components have no solubility in any of the photoconductive layer forming material and the information recording layer forming material.
Further, it is necessary that the material does not have conductivity. In the case of having conductivity, the space charge is diffused and the resolution is deteriorated, so that the insulating property is required. Further, since the dielectric layer applies a distribution voltage applied to the liquid crystal layer or deteriorates the resolution, it is preferable that the film thickness is small,
m or less. However, if the thickness is too small, image noise due to the interaction with time is generated, and there is a problem of permeation due to defects such as pinholes during lamination coating. Since the permeability due to defects such as pinholes differs depending on the solid content ratio of the material to be laminated, the type of solvent, and the viscosity, the thickness of the dielectric layer is appropriately set, but it is preferable that the thickness be at least 10 μm or less. Preferably, the thickness is 0.1 to 3 μm. Further, in consideration of the distribution of the voltage applied to each layer, a material having a high dielectric constant as well as a thin film is preferable.

As a material for forming the dielectric layer, inorganic materials such as SiO ₂ , TiO ₂ , CeO ₂ , Al ₂ O ₃ , G
eO ₂ , Si ₃ N ₄ , AlN, TiN, MgF ₂ , Zn
S, using a combination of silicon dioxide and titanium dioxide, a combination of zinc sulfide and magnesium fluoride, a combination of aluminum oxide and germanium, etc.
It is preferable to form the layers by a CVD method or the like. In addition, a water-soluble resin having low compatibility with an organic solvent, for example, an aqueous solution of polyvinyl alcohol, hydrogenated urethane, water glass, or the like is used, and a spin coating method, a blade coating method, a roll coating method, a bead coating method, a slide coating method is used. It may be laminated by a method or the like. Further, a coatable fluororesin may be used. In this case, the resin is dissolved in a fluorine-based solvent and applied by a spin coat method, or a blade coat method, a roll coat method, a bead coat method, a slide coat method, or the like. May be laminated. As a fluorine resin that can be applied,
For example, an organic material such as polyparaxylene which is formed into a film by a vacuum system and a fluororesin disclosed in JP-A-4-24722 can be preferably used.

Next, an information recording method according to the present invention will be described.

FIG. 11 is a diagram for explaining an information recording method in the first information recording device. The same applies to the second information recording device. In the figure, 11 is an information recording layer, 13
Is the electrode of the optical sensor, 13 'is the electrode of the information recording medium, 1
4 is a photoconductive layer, 21 is a light source, 22 is a shutter having a driving mechanism, 23 is a pulse generator serving as a power supply, 2
4 indicates a dark box.

When information light is incident from the light source 21 while applying an appropriate voltage between the electrodes 13 and 13 ′ by the pulse generator 23, the photoconductive layer 1 in the portion where the light is incident is formed.
The photocarrier generated in step 4 moves to the interface on the information recording layer 11 side by the electric field formed by the two electrodes, redistributes the voltage, and the liquid crystal layer in the information recording layer 11 is oriented according to the electric field or the amount of charge. Then, recording according to the pattern of the information light is performed.

In this information recording method, planar analog recording is possible, and recording at the liquid crystal level is obtained, so that high-resolution recording is achieved, and the exposure pattern is visualized by the orientation of the liquid crystal phase. Is held. The information recorded by the orientation of the liquid crystal is visible information that can be read visually, but it can be read by enlarging it with a projector, and the information is read with high precision using laser scanning or CCD. be able to.

[0101]

Embodiments of the present invention will be described below. In the following examples, "parts" or "%" indicates parts by weight or% by weight, respectively. Further, the following embodiments do not limit the contents of the present invention.

(Example 1) First light sensor Area resistance 8 formed on a glass substrate having a thickness of 1.1 mm
An ITO film having a thickness of 100 nm and a thickness of 0Ω / □ was sufficiently washed and dried.

On the ITO film, disclosed compound No. 71
To 1 part of polyvinyl butyral resin and 1,4-
After mixing with 98 parts of dioxane and 98 parts of cyclohexanone, the mixture was dispersed for 80 hours using a ball mill, and the particle size of the bisazo compound was determined by calculating the cumulative 50% average particle size [Nikkiso's “M
ICROTRAC2 ") was 0.21 μm. To this solution was added 0.24 part of chloranil in 1,4-
A solution dissolved in 0.88 part of dioxane and 0.88 part of cyclohexanone was added and mixed to obtain an ink. This ink is coated with a blade coater and air dried to 100
The resultant was dried at a temperature of 1 ° C. for 1 hour to form a charge generation layer having a thickness of 0.3 μm.

Next, 15 parts of p-diethylaminobenzaldehyde-N-phenyl-N-benzylhydrazone and 10 parts of a polycarbonate resin were placed on the charge generation layer.
1,1,2-trichloroethane: dichloroethane = 69
Part: 46 parts, and uniformly dissolved in a solvent consisting of 46 parts to obtain a coating solution, which was coated with a spinner at 500 rpm for 0.4 seconds. After coating, the film is left on the surface of the coating film in a windless state until the surface of the coating film is not adhered to the surface of the coating film, and then dried at 80 ° C. for 2 hours. Were laminated to produce an optical sensor having a photoconductive layer having a thickness of 10 μm.

(Electrical Characteristics of Optical Sensor) In order to measure the electrical characteristics of the obtained optical sensor, a gold electrode having a thickness of 0.16 cm ² , a thickness of 10 nm, and a surface resistance of 1 kΩ / □ was placed on the charge transport layer of the optical sensor. A current measuring device shown in FIG. 12 was formed by vapor deposition to form an electrode and a measurement medium.

In the figure, 15 is a photosensor support, 13 is a photosensor electrode, 16 is a concentration gradient region, 14 is a photoconductive layer,
Reference numeral 30 denotes a gold electrode, 31 denotes a light source, 32 denotes a shutter (No. 0 electromagnetic shutter manufactured by Copal Corporation), 33 denotes a shutter drive mechanism, 34 denotes a pulse generator (manufactured by Yokogawa Hewlett-Packard Company), and 35 denotes an oscilloscope.

In this current measuring device, the electrode 13 of the optical sensor is positive and the gold electrode is
0 V (1.5 × 10 ⁵ V / c electric field strength to optical sensor)
m) was applied, and 0.5 seconds after the start of the voltage application, light irradiation was performed from the glass substrate side for 0.033 seconds, and the light irradiation start time was set to t = 0, and the current flowing through the optical sensor was measured. The irradiation light was a green light obtained by a green filter (manufactured by Nippon Vacuum Optical Co., Ltd.) using a xenon lamp (L2274 manufactured by Hamamatsu Photonics) as a light source.
Irradiation at 1 ux intensity. The irradiation light intensity was measured with an illuminometer (manufactured by Minolta), and the characteristics of the filter used are shown in FIG.

The voltage application was continued after the light irradiation was completed, and the voltage application was continued for 0.15 seconds from the light irradiation start time. The result of measuring the time change of the current during that time with an oscilloscope is shown by the line A in FIG. The line B is a case where only a voltage is applied without exposure. The horizontal axis represents the voltage application time (second), and the vertical axis represents the current density (A / cm ² ). As shown by the line A, the current value has two inflection points (a).
(B) is observed. The amount of current below the inflection point (a) is considered to be a current (light-induced current) corresponding to the amount of exposure. Further, the inflection point (b) is a change point of the current amount following the end of the exposure, and it can be seen that the current according to the voltage change continuously flows and gradually attenuates even when the exposure is not performed yet. . That is, from this figure, it can be seen that, in the optical sensor of the present invention, the light-induced current continues to increase during exposure, continues after the exposure is completed, and gradually decreases after a certain period of time. The value of the base current density (passing current density in the unexposed portion) of this optical sensor was 5.5 × 10 ⁻⁶ A / cm ² .

The optical sensor of the present invention has a voltage of 10 ⁵ to 10 ⁶ V
When a voltage having an electric field strength of / cm is applied, the passing current density in the unexposed area is preferably 10 ⁻⁴ to 10 ⁻⁷ A / cm ² , whereby the amplification effect is remarkable and the information recording performance is reduced. It can be an excellent light sensor.

(Preparation of Information Recording Medium) An ITO film having a thickness of 100 nm was formed on a glass substrate having a thickness of 1.1 mm by sputtering, and after obtaining electrodes, the surface was cleaned.

On this electrode: 40 parts of a polyfunctional monomer (dipentaerythrol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.): 40 parts photocuring initiator (2-hydroxy-2-methyl- 1-phenylpropane-1-one, Ciba-Geigy, Darocure 1173) ... 2 parts,-Liquid crystal: 90% of smectic liquid crystal (Merck, S-6), nematic liquid crystal (Merck, E31LV) 50% of a coating solution obtained by uniformly dissolving 1 part of a surfactant (Florad FC-430, manufactured by Sumitomo 3M Limited) in 96 parts of xylene.
After coating using a blade coater with an interval of 0 μm, the coating film was dried at 47 ° C. for 3 minutes, then dried under reduced pressure at 47 ° C. for 2 minutes, and immediately cured by irradiation with 0.3 J / cm ² of ultraviolet light. Thus, an information recording medium having an information recording layer having a thickness of 6 μm was obtained.

After the liquid crystal was extracted from the surface of the information recording layer with hot methanol and dried, the internal structure was observed at 1000 times with a scanning electron microscope (S-800, Hitachi, Ltd.). 0.6 μm UV-curable resin, and inside the layer, a liquid crystal phase forming a continuous layer has a particle size of 0.1 μm.
m had a structure filled with a resin particle phase.

(Information Recording Method and Recording Characteristics) The obtained optical sensor and the information recording medium were combined as shown in FIG. 3, and an air layer was provided and opposed via a 10 μm-thick polyimide film spacer. Laminated.

As shown in FIG. 11, the laminated body was mounted on an imaging camera (RB67 manufactured by Mamiya Co.) instead of a photographic film, and 750 V was applied between both electrodes of the optical sensor and the information recording medium.
Was applied for 0.04 seconds, and at the same time, a projection exposure was performed from the optical sensor side for 1/30 seconds at a gray scale exposure of 2-200 lux. After the exposure, the information recording medium was taken out. When observing the information recording medium with transmitted light,
In the information recording layer, a recording portion composed of a light transmitting portion corresponding to a gray scale was observed.

Next, the information recorded on the information recording medium was read by an image scanner using a CCD line sensor, and the information was output using a sublimation transfer printer (SP-5500, manufactured by Victor Company of Japan). A good printed matter having a gradation property corresponding to the above was obtained.

When a color image was similarly recorded after being separated into three colors of R, G and B by a prism and a color filter, the recorded image was good. As a result, a good printed matter was obtained.

(Example 2) 5 parts by weight of polyvinyl alcohol (AT, manufactured by Shin-Etsu Chemical Co., Ltd., AT, saponification degree: 97 to 99) was formed on the photoconductive layer in the optical sensor manufactured in Example 1.
%) In 95 parts by weight of ion-exchanged water was applied by a spinner to form a 1 μm-thick dielectric layer.

Then, an information recording layer was formed on this dielectric layer in the same manner as in the method for forming the information recording layer shown in Example 1, and the information recording layer was formed on the information recording layer by sputtering.
Was deposited to a thickness of 20 nm to form a conductive layer, thereby producing an information recording medium.

At the same time as applying a DC voltage of 400 V between both electrodes of the information recording medium, the gray scale was projected and exposed from the optical sensor side for 1/30 second as in Example 1. The voltage application time was 0.05 seconds. After the exposure, the information recording medium was taken out and read and output by the same information output device as in Example 1. As a result, a good printed matter was obtained.

(Example 3) (Electrical characteristics of optical sensor) The electric characteristics of the optical sensor manufactured in Example 1 were measured 100 times. As a result, it was found that the optical sensor of the present invention was excellent in durability.

(Information Recording Characteristics)
The optical sensor and the information recording medium after repeating 00 times,
In the same manner as in Example 1, as shown in FIG.
An air layer was provided via a spacer of a polyimide film having a thickness of μm, and the layers were laminated to face each other.

As shown in FIG. 11, this laminated body was mounted on an imaging camera (RB67 manufactured by Mamiya) in place of a photographic film, and 700 mm was placed between the optical sensor and both electrodes of the information recording medium.
At the same time as applying a direct voltage of V for 0.04 seconds, the gray scale exposure amount is 2 to 200 lux for 1/30 seconds,
Projection exposure was performed from the light sensor side. After the exposure, the information recording medium was taken out. When the information recording medium was observed with the transmitted light, a recording portion including a light transmitting portion corresponding to a gray scale similar to that of Example 1 was observed in the information recording layer. Next, the information recorded on the information recording medium is read by an image scanner using a CCD line sensor, and the information is read by a sublimation transfer printer (SP- made by Victor Company of Japan, Ltd.).
5500), a good printed matter having the same gray scale gradation as in Example 1 was obtained.

Further, when a color image was recorded similarly after being separated into three colors of R, G and B by a prism and a color filter, the recorded image was good as in Example 1, and the recorded information of the color image was similar. As a result, good printed matter was obtained.

Example 4 Second optical sensor (Example of preparing imidazole perylene compound)
3,4,9,10-tetracarboxylic dianhydride 39.2
g, 32.4 g of o-phenylenediamine and 800 ml of α-chloronaphthalene were mixed and reacted at 260 ° C. for 6 hours. After cooling, the precipitated crystals were collected by filtration and washed repeatedly with methanol. Imidazole perylene compound (synthetic product) as a mixture of structural formulas (3) and (4) after drying by heating
g was obtained. The X-ray diffraction spectrum is shown in FIG.

The obtained imidazole perylene compound was
Under a pressure of 5 × 10 ^{-4 to} 5 × 10 ^-3 torr, 50
Sublimation purification was performed under heating conditions of 0 ° C. Volatile impurities were removed using a shutter. The obtained purified crystal was subjected to the same sublimation purification again to further purify (sublimated product). FIG. 15 shows the X-ray diffraction spectrum.

A solution obtained by dissolving 20 g of the obtained sublimated product in 600 ml of concentrated sulfuric acid was filtered through a glass filter.
It was dropped into 00 ml of pure water to precipitate. This was collected by filtration, washed sufficiently with pure water, and then dried (acid paste treated product). The X-ray diffraction spectrum is shown in FIG.

(Preparation of charge generation layer coating solution) Thickness 1.1 m
An ITO film having a sheet resistance of 80 Ω / □ and a film thickness of 100 nm formed on a glass substrate having a thickness of 100 m was sufficiently washed and dried.

As described in JP-A-7-261436, 3 parts of the above-mentioned acid paste-treated product and 1 part of polyvinyl butyral resin were mixed with 80 ml of methyl ethyl ketone, and subjected to a dispersion treatment for 80 hours by a ball mill.

FIG. 17 shows the results of measuring the X-ray diffraction spectrum of a part of the obtained dispersion liquid by concentrating and coagulating it. From the figure, the peak intensity at 12.4 ± 0.2 ° is maximum, the half width is 0.86 °, and 11.5 ± 0.2
It turns out that a clear peak is not shown in °.

By the dispersion treatment, the particle size of the imidazole perylene compound was reduced to a cumulative 50% average particle size [“MIC” manufactured by Nikkiso Co., Ltd.
A dispersion coating solution having a particle size of 0.21 μm was coated on the ITO film with a blade coater, air-dried, and dried at 100 ° C. for 1 hour to form a 0.3 μm-thick charge generation layer. And

Next, 15 parts of p-diethylaminobenzaldehyde-N-phenyl-N-benzylhydrazone and 10 parts of a polycarbonate resin were placed on the charge generation layer.
1,1,2-trichloroethane: dichloroethane = 69
Part: 46 parts, and uniformly dissolved in a solvent consisting of 46 parts to obtain a coating solution, which was coated with a spinner at 500 rpm for 0.4 seconds. After coating, the film is left on the surface of the coating film in a windless state until the surface of the coating film is not adhered to the surface of the coating film, and then dried at 80 ° C. for 2 hours. Were laminated to produce an optical sensor having a photoconductive layer having a thickness of 10 μm.

(Electrical Characteristics of Optical Sensor) In order to measure the electrical characteristics of the obtained optical sensor, a current measuring device shown in FIG. 12 was used under the same measurement conditions as in the case of the first optical sensor described above. FIG. 18 shows the measurement results. It can be seen that the second optical sensor has the same electrical characteristics as the first optical sensor. The value of the base current density (passing current density in the unexposed portion) of this optical sensor is 3.0 × 10 ^−6.
A / cm ² .

The optical sensor of the present invention has a voltage of 10 ⁵ to 10 ⁶ V
When a voltage having an electric field strength of / cm is applied, the passing current density in the unexposed area is preferably 10 ⁻⁴ to 10 ⁻⁷ A / cm ² , whereby the amplification effect is remarkable and the information recording performance is reduced. It can be an excellent light sensor.

The optical sensor manufactured as described above is combined with the information recording medium manufactured in Example 1 in the same manner as in Example 1 to form an information recording apparatus.
Was applied from the optical sensor side for 1/30 second at a gray scale exposure of 2-200 lux. After the exposure, the information recording medium was taken out. When observing the information recording medium with transmitted light,
In the information recording layer, a recording portion composed of a light transmitting portion corresponding to a gray scale was observed.

Next, the information recorded on the information recording medium was read by an image scanner using a CCD line sensor, and the information was output using a sublimation transfer printer (SP-5500, manufactured by Victor Company of Japan). A good printed matter having a gradation property corresponding to the above was obtained.

When a color image was recorded by separating the color into three colors of R, G, and B using a prism and a color filter, the recorded image was good. As a result, a good printed matter was obtained.

(Example 5) An information recording medium was manufactured by laminating a dielectric layer, an information recording layer, and a conductive layer on the optical sensor manufactured in Example 4 in the same manner as in Example 2.

A voltage of 350 V was applied between both electrodes of this information recording medium.
When a DC voltage of 0.05 second was applied and photographing, reading, and outputting were performed in the same manner as in Example 2, good printed matter was obtained.

[0139]

According to the photosensor of the present invention, a specific bisazo compound or an imidazole perylene compound having a specific crystal structure is contained in the photoconductive layer, so that the conductivity of the entire photosensor element is set to an appropriate state. Therefore, an optical sensor suitable for the operating voltage and range of the liquid crystal recording medium can be obtained. Therefore, the recording image density can be kept within a certain range, and stable recording of optical information can be performed. That is, the optical sensor according to the present invention can be an optical sensor having high sensitivity, stable electrical characteristics, good film properties, and little deterioration due to repeated use.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view for describing a first or second optical sensor of the present invention.

FIG. 2 is a cross-sectional view for explaining another example of each of the first and second optical sensors of the present invention.

FIG. 3 is a sectional view illustrating a first information recording device according to the present invention.

FIG. 4 is a sectional view illustrating a second information recording device according to the present invention.

FIG. 5 is a diagram showing a spectral characteristic of a green filter in a measurement system used for explaining a photocurrent amplifying action of the first or second optical sensor of the present invention.

FIG. 6 is a diagram showing a measurement result of a photocurrent amplifying action of a comparative sensor.

FIG. 7 is a diagram showing a change in quantum efficiency during light irradiation of a comparative sensor.

FIG. 8 is a diagram for explaining a photocurrent amplifying action in the optical sensor of the present invention.

FIG. 9 is a diagram for explaining a change in quantum efficiency during light irradiation of the optical sensor of the present invention.

FIG. 10 is a diagram showing definitions of a peak intensity and a half width at an X-ray diffraction peak.

FIG. 11 is a diagram for explaining an information recording method according to the present invention.

FIG. 12 is a diagram for explaining a current measuring device.

FIG. 13 is a diagram showing a current measurement result of the first optical sensor of the present invention.

FIG. 14 is an X-ray diffraction spectrum of an imidazole perylene compound (synthetic product).

FIG. 15 is an X-ray diffraction spectrum of an imidazole perylene compound (sublimated product).

FIG. 16 is an X-ray diffraction spectrum of an imidazole perylene compound (acid paste-treated product).

FIG. 17 is an X-ray diffraction spectrum of the imidazole perylene compound in Example 4.

FIG. 18 is a diagram showing a current measurement result of the second optical sensor of the present invention.

DESCRIPTION OF SYMBOLS 1 ... optical sensor, 2 ... information recording medium, 11 ... information recording layer, 13, 13 '... electrode, 14 is photoconductive layer, 14' ... charge generation layer, 14 "... charge transport layer, 15 ... Substrate, 19 ... Spacer, 20 ... Dielectric layer, 21 ... Light source, 22 ... Shutter with drive mechanism, 23 ... Pulse generator (power supply), 24 ... Dark box, 30 ... Gold electrode, 31 ... Light source, 32 ...
Shutter, 33 ... Shutter drive mechanism, 34 ... Pulse generator, 35 ... Oscilloscope

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // G03G 15/05 (72) Inventor Shinichi Hikosaka 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Hironori Ueyama 1-1-1, Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Daigo 1-1-1, Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Dai Nippon Printing stock Inside the company (72) Inventor Manabu Yamamoto 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd.

Claims (6)

[Claims] 1. An optical sensor having a photoconductive layer on at least an electrode, wherein the optical sensor is arranged to face an information recording medium having an information recording layer on at least the electrode, and a voltage is applied in a state where the voltage is exposed between both electrodes. Alternatively, in an optical sensor capable of forming information on an information recording medium by an electric field or a charge amount by exposing under an applied voltage, the photoconductive layer of the optical sensor is represented by the following general formula (1). An optical sensor comprising a bisazo compound. Embedded image In the formula, X ₁ and X ₂ each represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxy group, or a substituted or unsubstituted amino group. , X ₁ and X ₂
At least one of them is a halogen atom. p and q each represent an integer of 0, 1 or 2;
Are not simultaneously 0, and when p and q are 2, X ₁ and X ₂ may be the same or different groups. A represents a group represented by the following general formula (2). Embedded image (In the formula, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having a fluorinated hydrocarbon group. Z represents a substituted or unsubstituted aromatic carbocyclic group or an aromatic heterocyclic group. M and n each represent an integer of 0, 1 or 2. However, m and n do not become 0 at the same time. ｝ 2. An optical sensor having a photoconductive layer on at least an electrode, wherein the optical sensor is disposed so as to face an information recording medium having an information recording layer on at least the electrode, and a voltage is applied in a state where light is exposed between both electrodes. Or an optical sensor capable of forming information on an information recording medium by an electric field or a charge amount by exposing under an applied voltage, wherein the photoconductive layer of the optical sensor has the following structural formula (3) or An optical sensor comprising the imidazole perylene compound of the formula (4). Embedded image 3. The optical sensor is semi-conductive, and when a voltage is applied in a state where it is exposed between both electrodes, or when an exposure is performed in a state where a voltage is applied, an information recording medium is exposed to a current higher than a current caused by the exposure. It is possible to record information with the amplified intensity, and also shows a behavior that the conductivity gradually decreases when the voltage is continuously applied even after the exposure is completed, and has an effect of continuously recording information on the information recording medium. The optical sensor according to claim 1 or 2, wherein: 4. The method according to claim 1, wherein, when an electric field intensity of 10 ⁵ to 10 ⁶ V / cm is applied to the optical sensor, a passing current density in an unexposed portion is 10 ^-4 to 10 ^-7 A / cm ^2. The optical sensor according to any one of claims 1 to 3, wherein 5. An optical sensor having a photoconductive layer on at least an electrode and an information recording medium having an information recording layer on at least an electrode are arranged opposite to each other, and a voltage is applied between both electrodes in an exposed state. Or a photoconductive layer forming material in a photosensor capable of forming information on an information recording medium by an electric field or a charge amount by exposing under an applied voltage, and represented by the following general formula (1) A material for forming a photoconductive layer, comprising a bisazo compound. Embedded image In the formula, X ₁ and X ₂ each represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyano group, a hydroxy group, or a substituted or unsubstituted amino group. , X ₁ and X ₂
At least one of them is a halogen atom. p and q each represent an integer of 0, 1 or 2;
Are not simultaneously 0, and when p and q are 2, X ₁ and X ₂ may be the same or different groups. A represents a group represented by the following general formula (2). Embedded image (In the formula, Ar represents an aromatic carbocyclic group or an aromatic heterocyclic group having a fluorinated hydrocarbon group. Z represents a substituted or unsubstituted aromatic carbocyclic group or an aromatic heterocyclic group. M and n each represent an integer of 0, 1 or 2. However, m and n do not become 0 at the same time. ｝ 6. An optical sensor having a photoconductive layer on at least an electrode and an information recording medium having an information recording layer on at least an electrode are arranged opposite to each other, and a voltage is applied between both electrodes in an exposed state. Or a material for forming a photoconductive layer in an optical sensor capable of forming information on an information recording medium by an electric field or a charge amount by exposing under an applied voltage, and having the following structural formula (3) or structural formula (4) A material for forming a photoconductive layer, comprising the imidazole perylene compound. Embedded image